Nucleophilicity and leaving-group ability in frontside and backside S N2 reactions

Journal of Organic Chemistry

Volumn 73, Issue 18, 2008, Pages 7290-7299

  Bento, A Patrícia ^a   Bickelhaupt, F Matthias ^a  

^a VU UNIVERSITY AMSTERDAM   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; CHEMICAL REACTIONS; ELECTRONEGATIVITY; ELECTRONIC STRUCTURE;

CAUSAL RELATIONSHIPS; CHEMICAL EQUATIONS; HYPER-POLARIZABILITY; NUCLEOPHILIC SUBSTITUTIONS; NUCLEOPHILICITY;

ELECTROCHEMICAL PROPERTIES;

BROMINE; CHLORINE; FLUORINE; IODINE;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; DENSITY FUNCTIONAL THEORY; ENERGY TRANSFER; REACTION ANALYSIS;

EID: 52449097758     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo801215z     Document Type: Article

References (69)

1. (a) Smith, M. B.; March, J. March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure; Wiley: New York, 2007.
2. (b) Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, Part A; Springer: New York, 2007.
3. (c) Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry; Harper and Row: New York, 1987.
4. (d) lngold, C. Structure and Mechanism in Organic Chemistry; Cornell University Press: Ithaca, NY, 1969.
5. Angel, L. A.; Ervin, K. M. J. Phys. Chem. A 2001, 105, 4042.
6. (a) Angel, L. A.; Ervin, K. M. J. Phys. Chem. A 2004, 108, 9827.
7. (b) Bach, R. D.; Dmitrenko, O.; Thorpe, C. J. Org. Chem. 2008, 73, 12.
8. (c) Botschwina, P. Theor. Chem. Acc. 1998, 99, 426.
9. (d) Carvalho, A. T. P.; Swart, M.; van Stralen, J. N. P.; Fernandes, P. A.; Ramos, M. J.; Bickelhaupt, F. M. J. Phys. Chem. B 2008, 112, 2511.
10. (e) Chabinyc, M. L.; Craig, S. L.; Regan, C. K.; Brauman, J. I. Science 1998, 279, 1882.
11. (f) Chandrasekhar, J.; Smith, S. F.; Jorgensen, W. L. J. Am. Chem. Soc. 1985, 107, 154.
12. (g) DePuy, C. H.; Gronert, S.; Mulin, A.; Bierbaum, V. M. J. Am. Chem. Soc. 1990, 112, 8650.
13. (h) Glukhovtsev, M. N.; Pross, A.; Radom, L. J. Am. Chem. Soc. 1995, 117, 2024.
14. (i) Glukhovtsev, M. N.; Pross, A.; Radom, L. J. Am. Chem. Soc. 1996, 118, 6273.
15. (j) Glukhovtsev, M. N.; Pross, A.; Schlegel, H. B.; Bach, R. D.; Radom, L. J. Am. Chem. Soc. 1996, 118, 11258.
16. (k) Gonzales, J. M.; Pak, C.; Cox, R. S.; Allen, W. D.; Schaefer, H. F., III; Császár, A. G.; Tarczay, G. Chem. - Eur. J. 2003, 9, 2173.
17. (l) Gronert, S. Acc. Chem. Res. 2003, 36, 848.
18. (m) Harder, S.; Streitwieser, A.; Petty, J. T.; Schleyer, P. v. R. J. Am. Chem. Soc. 1995, 117, 3253.
19. (n) Laerdahl, J. K.; Uggerud, E. Int. J. Mass Spectrom. 2002, 214, 277.
20. (o) Lee, I.; Kim, C. K.; Sohn, C. K.; Li, H. G.; Lee, H. W. J. Phys. Chem. A 2002, 106, 1081.
21. (p) Li, C.; Ross, P.; Szulejko, J. E.; McMahon, T. B. J. Am. Chem. Soc. 1996, 118, 9360.
22. (q) Nibbering, N. M. M. Acc. Chem. Res. 1990, 23, 279.
23. (r) Norton, S. H.; Bachrach, S. M.; Hayes, J. M. J. Org. Chem. 2005, 70, 5896.
24. (s) Ren, Y.; Yamataka, H. Chem. Eur. J. 2007, 13, 677.
25. (t) Schmatz, S. ChemPhysChem 2004, 5, 600.
26. (u) Schmatz, S.; Botschwina, P.; Stoll, H. Int. J. Mass Spectrom. 2000, 201, 277.
27. N2 Mechanism; Wiley: New York, 1992.
28. (w) Su, T.; Wang, H.; Hase, W. L. J. Phys. Chem. A 1998, 102, 9819.
29. (x) van Bochove, M. A.; Bickelhaupt, F. M. Eur. J. Org. Chem. 2008, 649.
30. (y) van Bochove, M. A.; Swart, M.; Bickelhaupt, F. M. J. Am. Chem. Soc. 2006, 128, 10738.
31. (z) van Bochove, M. A.; Swart, M.; Bickelhaupt, F. M. ChemPhysChem 2007, 8, 2452.
32. (aa) Vayner, G.; Houk, K. N.; Jorgensen, W. L.; Brauman, J. I. J. Am. Chem. Soc. 2004, 126, 9054.
33. (bb) Wang, H.; Hase, W. L. J. Am. Chem. Soc. 1997, 119, 3093.
34. (cc) Wladkowski, B. D.; Allen, W. D.; Brauman, J. I. J. Phys. Chem. 1994, 98, 13532.
35. (dd) Uggerud, E. Chem. - Eur. J. 2006, 12, 1127.
36. Bento, A. P.; Bickelhaupt, F. M. J. Org. Chem. 2007, 72, 2201.
37. Bickelhaupt, F. M. J. Comput. Chem. 1999, 20, 114.
38. (a) Deng, L.; Branchadell, V.; Ziegler, T. J. Am. Chem. Soc. 1994, 116, 10645.
39. (b) Bickelhaupt, F. M.; Hermann, H.; Boche, G. Angew. Chem. 2006, 118, 838;
40. Angew. Chem., Int. Ed. 2006, 45, 823.
41. Olmstead, W. N.; Brauman, J. I. J. Am. Chem. Soc. 1977, 99, 4219.
42. Bento, A. P.; Bickelhaupt, F. M. Chem. Asian J. 2008, 3, in press.
43. According to the IUPAC Gold Book, nucleophilicity is the relative reactivity of nucleophilic reagent and the leaving-group ability (nucleofugality) is the tendency of atoms or groups to depart with the bonding electron pair.
44. Computer code ADF 2007.01; Baerends, E. J. SCM: Amsterdam, The Netherlands; Fonseca Guerra, C.; Snijders, J. G.; te Velde, G.; Baerends, E. J. Theor. Chem. Acc. 1998, 99, 391.
45. (a) Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41.
46. (b) te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.; Fonseca Guerra, C.; van Gisbergen, S. J. A.; Snijders, J. G.; Ziegler, T. J. Comput. Chem. 2001, 22, 931.
47. van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1994, 101, 9783.
48. (a) Handy, N. C.; Cohen, A. J. Mol. Phys. 2001, 99, 403.
49. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
50. (a) Baker, J.; Pulay, P. J. Chem. Phys. 2002, 117, 1441.
51. (b) Bento, A. P.; Sola, M.; Bickelhaupt, F. M. J. Comput. Chem. 2005, 26, 1497.
52. (c) Gonzales, J. M.; Allen, W. D.; Schaefer, H. F., III J. Phys. Chem. A 2005, 109, 10613.
53. (d) Grüning, M.; Gritsenko, O. V.; Baerends, E. J. J. Phys. Chem. A 2004, 108, 4459.
54. (e) Swart, M.; Ehlers, A. W.; Lammertsma, K. Mol. Phys. 2004, 102, 2467.
55. (f) Xu, X.; Goddard, W. A., III J. Phys. Chem. A 2004, 108, 8495.
56. Fan, L.; Versluis, L.; Ziegler, T.; Baerends, E. J.; Ravenek, W. Int. J. Quantum Chem. Quantum Chem. Symp. 1988, S22, 173.
57. Fan, L.; Ziegler, T. J. Chem. Phys. 1990, 92, 3645.
58. Fukui, K. Acc. Chem. Res. 1981, 14, 363.
59. (a) de Jong, G. Th.; Bickelhaupt, F. M. ChemPhysChem 2007, 8, 1170.
60. (b) Diefenbach, A.; Bickelhaupt, F. M. J. Chem. Phys. 2001, 115, 4030.
61. (c) Diefenbach, A.; de Jong, G. Th.; Bickelhaupt, F. M. J. Chem. Theory Comput. 2005, 1, 286.
62. Baerends, E. J.; Gritsenko, O. V. J. Phys. Chem. A 1997, 101, 5383.
63. Bickelhaupt, F. M.; Baerends E. J. In Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B., Eds.; Wiley-VCH: New York, 2000; Vol. 15, pp 1-86.
64. (a) Bickelhaupt, F. M.; Nibbering, N. M. M.; van Wezenbeek, E. M.; Baerends, E. J. J. Phys. Chem. 1992, 96, 4864.
65. (b) Bickelhaupt, F. M.; Diefenbach, A.; de Visser, S. P.; de Koning, L. J.; Nibbering, N. M. M. J. Phys. Chem. A 1998, 102, 9549.
66. (c) Ziegler, T.; Rauk, A. Theor. Chim. Acta 1977, 46, 1.
67. (d) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1558.
68. (e) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1755.
69. Anh, N. T.; Minot, C. J. Am. Chem. Soc. 1980, 102, 103.